Surface-coating compositions containing polyoxymethyleneoxazolidines

ABSTRACT

Surface-coating compositions that have improved resistance to attack by bacteria and fungi contain 0.1 percent to 3 percent by weight of a biocidal component that comprises a polyoxymethyleneoxazolidine selected from the group consisting of A. COMPOUNDS HAVING THE STRUCTURAL FORMULA   WHEREIN EACH R represents hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, halophenyl, or -(CH2O)mCH2OH; m represents a number in the range of 0 to 2; and n represents a number in the range of 1 to 4; B. COMPOUNDS HAVING THE STRUCTURAL FORMULA   D R A W I N G WHEREIN EACH R&#39;&#39; represents alkyl of 1 to 6 carbon atoms or CH2OH and R and n have the aforementioned significance; and C. MIXTURES THEREOF. The polyoxymethyleneoxazolidines preferably contain a total of not more than six oxymethylene units (-CH2O-) in one or more ring substituents.

United States Patent [191 Sidi et all.

[ June 17, 1975 [75] Inventors: Henri Sidi, Paramus; Hilding R.

Johnson, Wayne, both of NJ.

[73] Assignee: Tenneco Chemicals, Inc., Saddle Brook, NJ.

[22] Filed: Mar. 4, 1974 [21] Appl. No.: 447,797

[521 US. Cl 260/29.6 HN; 260/45.8 NZ [51] Int. Cl. C08f 45/60 [58] Field ofSearch 260/45.8 NZ, 307 FA,

[56] References Cited UNITED STATES PATENTS 2,571,985 10/1951 Carnes 260/307 2,752,357 6/1956 Watanabe 260/307 2,778,825 1/1957 Melamed 260/244 2,999,047 9/1961 Model et al.... 424/272 3,256,137 6/1966 Danielson 260/307 3,595,817 7/1971 Deinet 260/22 3,679,622 7/1972 Grier 260/29.7 3,725,327 4/1973 Stearns et a1. 260/29.6

Primary Examiner-M. .1. Welsh Attorney, Agent, or Firm Evelyn Berlow [57] ABSTRACT Surface-coating compositions that have improved resistance to attack by bacteria and fungi contain 0.1 percent to 3 percent by weight of a biocidal component that comprises a polyoxymethyleneoxazolidine selected from the group consisting of a. compounds having the structural formula IH O (CH O) CH OH 1 O N O R it wherein each R represents hydrogen, alkyl of l to 6 carbon atoms, phenyl, halophenyl, or (CH O),,,C- H Ol-l; m represents a number in the range of 0 to 2; and n represents a number in the range of 1 to 4;

b. compounds having the structural formula wherein each R represents alkyl of 1 to 6 carbon atoms or CH OH and R and n have the aforementioned significance; and

c. mixtures thereof.

The polyoxymethyleneoxazolidines preferably contain a total of not more than six oxymethylene units (CH O--) in one or more ring substituents.

18 Claims, No Drawings SURFACE-COATING COMPOSITIONS CONTAINING POLYOXYMETHYLENEOXAZOLHDHNES This invention relates to surface-coating composi tions that have improved resistance to deterioration resulting from attack by bacteria, fungi, and other microorganisms. More particularly, it relates to surfacecoating compositions that contain a biocidally-effective amount of a polyoxymethyleneoxazolidine.

lt is well known in the art that paints and varnishes often have inadequate resistance to the action of mircroorganisms. Some of these coating compositions, such as enamels and house paints, contain as their resinous binders drying oils, oleoresinous varnishes, or alkyl resins, which are subject to attack by fungi and bacteria. Others, for example, aqueous dispersions of water-insoluble synthetic linear polymers, generally contain as plasticizers and thickeners materials that have their origin in animal or vegetable sources and that render the compositions susceptible to mildew. The resulting deterioration of the surface-coating compositions seriously hinders their full scale utilization, particularly in those areas and in those applications that are conducive to such attack.

Various biocidal materials have been suggested for use in surface-coating compositions, but none has proven entirely satisfactory in this application. Some do not provide the required prolonged protection against attack by microorganisms, while others undergo sulfide staining and still others hydrolyze in alkaline aqueous paint systems or separate from the applied coating by migration, volatilization, or leaching after the coating has been spread in a thin layer over the surface to be protected. Some biocidal materials cause the coating compositions to gel or impart color or odor to them.

This invention relates to biocides that are of particular value in surface-coating compositions. These biocides, which are thoroughly compatible with the resinous binders that commonly are used in surface-coating compositions and which are resistant to sulfide staining, provide excellent and prolonged resistance to deterioration resulting from attack by bacteria, fungi, and other microorganisms without adversely affecting the color, pH. viscosity, and other physical properties of the surface-coating compositions.

The biocidal compounds that are used in the surfacecoating compositions of this invention are a. compounds having the structural formula rn oicn oi cu on wherein each R represents hydrogen, alkyl of l to 6 carbon atoms, phenyl, halophenyl, or (CH O),,,C- H OH; m represents a number in the range of to 2; and n represents a number in the range of l to 4',

b. compounds having the structural formula I l l wherein each R represents alkyl of 1 to 6 carbon atoms or CH OH, and R and n have the aforementioned significance; and

c. mixtures of these compounds.

Illustrative of the bicyclic polyoxymethyleneoxazoli' dines of this invention are the following: 5- [hydroxymethyl-di(oxymethylene)]-l-aza-3,7-dioxabicyclo(3,3,0)octane, S-[hydroxymethyltri(oxymethylene)]-1-aza-3,7-dioxabicyclo(3,3,0)octane, 2'phenyl-5-[hydroxymethyltetra(oxymethylene)]-1-aza-3,7-dioxabicyclo(3,3,0)- octane. 2,8-bis(a-chloroethyl)-5-[hydroxymethylpenta(oxymethylene)]-1-aza3 ,7-dioxabicyclo( 3,3,- 0)octane, 2,8-bis(p-chlorophenyl)-5-[hydroxymethyltri(oxymethylene)]-l-aza3,7-dioxabicyclo(3,3,0)octane, Z-hydrQXymethyI-SIhydroxymethyltetra(oxymethylene l -aza-3 ,7-dioxabicyclo( 3,3 0)octane, 2,8-bis(2 ethylbutyl)-5-[hydroxymethyltri(oxymethylene)]-1-axa-3,7-dioxabicyclo(3,3,0)octane, and 2,8-bis(hydroxymethyl)-5-[hydroxymethyldi(oxymethylene)]-1-aza-3,7-dioxabicyclo(3,3,0)octane. Examples of the monocyclic polyoxymethyleneoxazolidines include 3- hydroxymethyloxymethylene-4,4-dimethyloxazolidine, 3-[hydroxymethyl-di(oxymethylene)]-4,4- diethyloxazolidine, 3-[hydroxymethyltri(oxymethylene)]-4,4-diethyloxazolidine, 3- [hydroxymethyl-tetra(oxymethylene)1-4-methyl-4- isopropyloxazolidine, 2-hexyl-3-[hydroxymethyltri( oxymethylene) ]-4,4-di( hydroxymethyl )oxazolidine, 2-phenyl-3-[hydroxymethyl-di(oxymethylene)]- 4-hexyl-4-hydroxymethyloxazolidine, 2-pchlorophenyl-3-(hydroxymethyloxymethylene)-4,4- di(hydroxymethyl)oxazolidine, 2-hydroxyrnethyl-3- [hydroxymethyl-di(oxymethylene)]-4,4-

dibutyloxazolidine, and 2,3- bis(hydroxyrnethyloxymethylene)-4,4- dimethyloxazolidine.

The preferred compounds for use in surface-coating compositions are those in which the total number of oxymethylene (-CH O) units in one or more of the substituents on the oxazolidine ring is not greater than six. While compounds having more than six oxymethylene units in their ring substituents are very effective in controlling the growth of bacteria and fungi, they tend to be somewhat unstable in surface-coating compositions and to impart to them the odor of formaldehyde. Examples of the preferred bicyclic compounds include polyoxymethyeneoxazolidines in which i. the substituent in the 5-position is (CH O(C- H O) ..,CH OH and the substituents in the 2 and 8- positions are hydrogen, alkyl, phenyl, or halophenyl;

ii. the substituent in the 5-position is CH OCl-l- OCH OH, that in the 2-position is (CH O) CH OH, and that in the 8position is hydrogen, alkyl, phenyl, or halophenyl;

iii. the substituent in the -position is -CH O(C- H O) -CH OH and the substituents in the 2- and 8- positions are CH OH.

Examples of the preferred monocyclic compounds include polyoxymethyleneoxazolidines in which i. the substituent in the 2-position is hydrogen, alkyl, phenyl, or halophenyl, that in the 3-position is (C- H O) -CH OH, and those in the 4-position are alkyl;

ii. the substituent in the 2-position is ---(Cl-i O) Cl-l OH, that in the 3-position is CH OCH OH, and those in the 4-position are alkyl;

iii. the substituent in the 2-position is CH Ol-l, that in the 3-position is (CH O) CH OH, and one or both of those in the 4-position are Cl-l OH.

The biocidal compounds of this invention may be prepared by any suitable and convenient procedure. For example, they may be prepared by the reaction of the appropriate oxazolidine with formaldehyde and/or paraformaldehyde. Alternatively, they may be prepared by the reaction of an aminoalcohol with formaldehyde and/or paraformaldehyde and optionally another aldehyde. These reactions are ordinarily carried out in aqueous solution at a temperature between about and 100C. When an aqueous formaldehyde solution is used, the reactions are preferably carried out at ambient temperature; when paraformaldehyde or a mixture of aqueous formaldehyde and paraformaldehyde is used, it is preferred that the reaction be carried out at a higher temperature.

Among the aminoalcohols that can be reacted with formaldehyde and, if desired, another aldehyde to form the novel polyoxymethyleneoxazolidines are Z-amino- Z-methylpropanoll Z-amino-Z-ethylpropanol-l, 2- amino-1,3-propanediol, 2-amino-2-methyll ,3' propanediol, 2-amino-2-ethyl-l,3-propanediol, 2- amino-2-butyl-l,3-propanediol, and tris(hydroxymethyl)aminomethane. The aminoalcohol is reacted with formaldehyde or a mixture of formaldehyde and a second aldehyde. The second aldehyde may be an aliphatic aldehyde, such as acetaldehyde, a-chloroacetaldehyde, propionaldehyde, butyraldehyde, or 2- ethylbutyraldehyde; an aromatic aldehyde, such as benzaldehyde, p-chlorobenzaldehyde, or 2,4- dichlorobenzaldehyde; a dialdehyde, such as glyoxal, succinaldehyde, or glutaraldehyde; or a mixture of these aldehydes.

The reaction products may be recovered from the aqueous solutions in which they are formed and purified by known techniques. In most cases the products are mixtures comprising polyoxymethyleneoxazolidines having the structural formulas set forth hereinbefore.

Particularly advantageous results have been obtained when the aqueous solutions of polyoxymethyleneoxazolidines resulting from the reactions previously described are used without separation or purification of the biocidal compound or additional treatment other than adjustment of the concentration of the biocidal component to the desired level to protect surfacecoating compositions from attack by bacteria and fungi. in addition to costing less than the purified polyoxymethyleneoxazolidines and being easier to incorporate into aqueous surface-coating compositions, the aqueous solutions, which contain 20 to 80 percent and preferably 40 to 60 percent by weight of one or more of the aforementioned polyoxymethyleneoxazolidines, provide better biocidal activity for a given concentration of the polyoxymethyleneoxazolidine in the surface-coating composition. Unlike most other aqueous surface-coating compositions that contain a biocide, the surface-coating compositions to which the aqueous polyoxymethyleneoxazolidine solutions have been added tend to become lighter in color on aging.

The polyoxymethyleneoxazolidines of this invention can be used to impart bacterial and fungal resistance to a wide variety of surface-coating compositions including both water-based and organic solvent-based coating systems.

In a preferred embodiment of the invention, the polyoxymethyleneoxazolidines are used as the biocide in aqueous surface-coating compositions that contain about 10 to 60 percent by weight of a water-insoluble, film-forming, resinous binder that is an oleoresinous binder, a synthetic linear addition polymer, or a mixture of these binders. The useful aqueous dispersions of synthetic linear addition polymers are ordinarily prepared by the emulsion polymerization of ethylenicallyunsaturated monomers. lllustrative of these polymers are polyvinyl acetate; polyvinyl butyrate; polyvinyl chloride; copolymers of vinyl acetate with vinyl chloride or acrylonitrile; copolymers of vinyl chloride with vinylidene chloride; polyethylene; polyisobutylene; polystyrene; copolymers of styrene with maleic anhydride or butadiene; copolymers of acrylonitrile with butadiene; copolymers of methacrylic acid esters of alcohols having 1 to 8 carbon atoms with vinyl acetate, vinyl chloride, acrylonitrile, or styrene; copolymers of acrylic acid esters of alcohols having 1 to 8 carbon atoms with vinyl acetate, vinyl chloride, acrylonitrile, or sytrene; and mixtures thereof. Suitable oleoresinous binders include drying oils, such as linseed oil, tung oil, soybean oil, dehydrated castor oil, safflower oil, or fish oil; bodied drying oils; blends of drying oils or bodied drying oils with a resin component such as limed rosin, an ester gum, or phenolic resin; oleoresinous varnishes formed by heating one of the aforementioned resins with one or more drying oils or bodied drying oils; alkyd resins, which are resinous products resulting from the reaction of a polyhydric alcohol, such as pentaerythritol or glycerol, with a dicarboxylic acid, such as phthalic anhydride, and fatty acids; and mixtures thereof.

The polyoxymethyleneoxazolidines can also be used as the biocide in organic solvent-based systems that contain an oleoresinous binder as hereinbefore defined.

The addition to surface-coating compositions of as little as 0.1 percent by weight of one or more of the biocidal compounds of this invention will bring about an appreciable improvement in the resistance of the composition to attack by fungi and bacteria. Three percent or more of the biocidal compounds can be used, but these larger amounts ordinarily do not provide further improvement in the properties of the surface-coating compositions and for this reason are not usually used. The amount of the biocidal compound that will provide optimum protection for a surface-coating composition depends upon such factors as the choice of the biocidal compound, the choice of resinous binder and other ingredients of the composition and the amount of each of these materials that is used, and the application for which the coating composition is intended. In most cases 1 to 2 percent of polyoxymethyleneoxazolidine, based on the weight of the composition, is used to protect surface-coating compositions from attack by fungi. From 0.1 percent to 0.5 percent of a polyoxymethyleneoxazolidine, based on the weight of the composition, is preferably incorporated into aqueous surfacecoating compositions to protect them from attack by bacteria.

In addition to the resinous binder and the biocidal compound, the surface-coating compositions may contain various auxiliary materials, such as pigments, extenders, solvents, dyes, defoaming agents, driers, thickeners, emulsifiers, plasticizers, other biocides, and the like in the amounts ordinarily used for these purposes.

The biocidal compounds may be incorporated into the surface-coating compositions by any suitable procedure. As has been indicated hereinbefore, the best results are obtained when aqueous solutions of the polyoxymethyleneoxazolidines are added to aqueous surface-coating compositions. Alternatively, the biocidal compounds can be combined with the pigments and other components to form a pigment phase that is mixed with the resinous binder and water or organic solvent to form the surface-coating composition.

The invention is further illustrated by the following examples.

EXAMPLE 1 A mixture of 60.5 grams (0.5 mole) of tris(hydroxymethyl)aminomethane, 121.5 grams (1.5 moles) of 37% aqueous formaldehyde solution, and 31.6 grams (1.0 mole) of 95% paraformaldehyde was stirred and heated at its reflux temperature until a homogeneous solution was obtained. The solution was cooled and filtered. There was obtained 213 grams of a clear yellow solution that contained 43.1% of water and 56.9% of solids. The pH of an 0.1 M solution of the product was 6.6. The product was shown by NMR, IR, and GC analysis of its silyl ethers to be a mixture of 5- hydroxymethyl-l -aza-3,7-dioxabicyclo( 3 ,3 ,0 )octane, S-hydroxymethoxymethyll -aza-3,7-dioxabicyclo( 3,3,- )octane. and 5-hydroxymethylpolyoxymethylene-1- aza-3,7-dioxabicyclo(3,3,0)octanes having the structural formula (H 0 (CII O) cn ou t ii: L CH2 5 o 0112 611 wherein x represents numbers in the range of l to 3.

EXAMPLE 2 analysis of its silyl ethers to be a mixture containing about 20% of S-hydroxymethyl-1-aza-3,7-dioxabicyclo(3,3,0)octane, 37% of 5-hydroxymethoxymethyl-1- aza-3,7-dioxabicyclo(3,3,0)octane, 14% of 5- [hydroxymethyl-di( oxymethylene 1 -aza-3 ,7-dioxabicyclo(3,3,0)octane, 21% of S-[hydroxymethyltri(oxymethylene)]- 1 -aza-3,7-dioxabicyclo( 3 ,3 ,0 )octane, and 8% of 5-[hydroxymethyltetra(oxymethylene 1 -aza-3 ,7-dioxabicyclo( 3,3 0)octane.

EXAMPLE 3 A mixture of 29.0 grams (0.2 mole) of 5- hydroxymethyll -aza-3 ,7-dioxabicyclo( 3 ,3 ,0 )octane and 32.4 grams (0.4 mole) of 37% aqueous formaldehyde solution was stirred at ambient temperature until a homogeneous solution was obtained. The product was an aqueous solution that contained 26.1% of water and 73.9% of 5-[hydroxymethyl-di(oxymethylene)]-laza-3,7-dioxabicyclo(3,3,0)octane. The pH of an 0.1 M solution of the product was 6.9.

EXAMPLE 4 A mixture of 20.2 grams (0.2 mole) of 4,4- dimethyloxazolidine and 32.4 grams (0.4 mole) of 37% aqueous formaldehyde solution was stirred at ambient temperature until a homogeneous solution was obtained. The product was an aqueous solution that contained 31.5% of water and 68.5% of 3- hydroxymethyloxymethylene-4,4-dimethyloxazolidine. The pH of an 0.1 M solution of the product was 9.8.

EXAMPLE 5 A mixture of 20.2 grams (0.2 mole) of 4,4- dimethyloxazolidine, 32.4 grams (0.4 mole) of 37% aqueous formaldehyde solution, and 6.3 grams (0.2 mole) of paraformaldehyde was stirred and heated at its reflux temperature until a homogeneous solution was obtained. The solution was cooled and filtered. The resulting clear solution contained 36.6% of water and 63.4% of solids. The ph of an 0.1 M solution of the product was 10.7. The product was shown by NMR analysis to be a mixture of poly(oxymethylene)-4,4- dimethyloxazolidines containing a major amount of 3- [hydroxymethyl-di(oxymethylene)]-4,4- dimethyloxazolidine.

EXAMPLE 6 A mixture of 20.2 grams (0.2 mole) of 4,4- dimethyloxazolidine, 48.7 grams (0.6 mole) of 37% aqueous formaldehyde solution, and 6.3 grams (0.2 mole) of 95% paraformaldehyde was stirred and heated at its reflux temperature until a homogeneous solution was obtained. The solution was cooled and filtered. lt contained 40.4% of water and 59.6% of solids. The pH of an 0.1 M solution of the product was 10.3. The product was shown by analysis to be a mixture of po1y(oxymethylene)-4,4-dimethyloxazolidines containing a major amount of 3- [hydroxymethyltri( oxymethylene) ]-4,4- dimethyloxazolidine.

EXAMPLE 7 A. A polyvinyl acetate latex paint was prepared by mixing together the following materials:

Parts by Weight Wat r 481.5 25% Aqueous solution of sodium salt of maleic anhydride/diisobutylene copolymer 24 Potassium pyrophosphate 3 Long chain fatty acid alkanolamide 9 Defoamer 6 Ethylene glycol 75 l-%% Aqueous solution of hydroxyethylcellulose 375 Aqueous emulsion containing 55% of polyvinyl acetate l299 Diethyl ether of diethylene glycol 30 Titanium dioxide 690 Talc 345 Calcium metasilicate 150 This paint had the following properties as determined by standard paint testing procedures:

Viscosity 65 K.U. Brookfield Viscosity (No. 4 spindle, 60 rpm) 800 cps. p 7.8 Yellowness index 3.0

Small amounts of the biocidal compounds of this invention or comparative biocides were added to portions of this paint.

B. An acrylic latex paint was prepared by mixing together the following materials:

- Continued Parts by Weight This paint had the following properties:

Viscosity 72 K.U. Brookfield Viscosity (No. 3 I250 spindle. 60 rpm) (cps) Yellowness index 10 Small amounts of the biocidal compounds of this invention or comparative biocides were added to portions of this paint.

C. An exterior house paint was prepared by mixing is together the followingmaterials:

Parts by Weight Lead naphthenate (24%) Small amounts of the biocidal compounds of this invention or comparative biocides were added to portions of this paint. I

D. The polyvinyl acetate'latex paint, the acrylic latex paint, and the oil-based paint were evaluated by means of an agar diffusion assay. ln this test, agar is inoculated with the test organism, the treated paint is placed in a Parts well cut from the agar, and after mcubation at 28C. by weght and 85-95% relative humidity, the activity of the'biowater 68 cide is measured by zones of inhibition. The biocidal z s y i ether f r n d l f 6 compounds tested and the results obtained are given in 0. queous so utlon 0 so tum sa t o maleic anhydride/diisobutylene copolymer 27 the table that follows In thls table Defoamer 12 4Q 2% Aqueous solution of hydroxyethyl- 300 cellulose ZO Zone of inhibited growth in mm. Ethylene glycol 60 O No zone of inhibition; no growth Titanium dioxide 750 Tr Trace zone of inhibited growth Mica (waterground) 9U Not tested Calcium carbonate 375 Bacteria A Mixed paint spoilage strains Ammonium hydroxide (28%) 6 B Pseudomonas aeruginosa Aqueous dispersion containing 46% acrylic 1642 C Aerobacter aerogenes ester copolymer (6671 ethyl acrylate, Fungi D Pullularia pullulans 32.5% methyl acrylate. and 1.5% E Penicillium crustosum acrylic acid) F Aspergillus niger Table Activity of Polyoxymethyleneoxazolidines as Biocides in Paints Test Biocidal Activity Level Effect on Liquid Paint Bacteria Fungi Biocide Paint 76) pH Odor Color Viscosity A B C D E F Product of Ex. 1 PVA 2 7.3 None None None Z0 20 ZO-lO ZO-l4 20-20 20-9 20-2 1 7.4 ZO-l7 20-8 ZO-lO ZO-lO ZO-S 20-] (1.5 7.4 ZO-l5 ZO-5 ZO-8 ZO-S ZO-S 0 0.1 7.4 ZO-7 ZO-3 20-1 0 0 0 Acrylic 2 7.7 Gelled ZO-24 ZO-9 ZO-lO ZO-l9 20-7 20-! l 7.9 None 20-] l 202 ZO-4 ZO-3 ZO-4 Tr 0.5 8.5 ZO-S Tr ZO-l O t O 0 0.l 9.l 0 O 0 0 0 0 Oil 2 ZO 4 ZO-3 ZO-2 Product of Ex. 2 PVA 2 7.3 None None None ZO-22 ZO-l4 ZO-l4 ZO-3O ZO-l l ZO-3 l 7.4 ZO-l8 ZO-S ZO-l4 ZO-lO ZO-8 Z0- 0.5 7.4 Z045 ZO-7 ZO l l ZO-S ZO-S Tr ().l 7.4 ZO-7 ZO-4 'ZO-5 Tr ZO-l 0 Acrylic 2 7.6 Z0 20 ZO-9 ZO-l 3 20-21 ZO-9 20-}! l 7 r8 ZO l 2 ZO-4 ZO-7 ZO-S ZO-4 Tr 0.5 8.4 ZO7 20-2 20-1 Tr O O 0.1 9.l Tr O O O 0 0 O 2 H .1 20 7 ZOS ZO-3 Table Continued Acti\ ity of Polyoxymethyleneoxazolidines us Blocidcs in Paints lest Biocidzll Activity Level Effect on Liquid Paint Bacteria Fungi Biocide Paint ('4 pH OLlOl' Color \"iscosily A B D E F Product of Ex. 3 PVA 2 6.8 None None (iellcd Z-l5 20-8 7.0-10 ZO-ZO 7.0-8 7.0-1

l 7.2 None ZO-lS ZO-'-) ZO-9 ZO-l-i 20-5 'lr 0.5 7.1 ZO-l3 20-7 ZO-X Z04; 7.0-3 'l'r 0.1 7.5 20-6 2.0-2 Tr 0 u 0 Acrylic I 7.3 20- l 4 7.0-7 20-9 20- l 20-8 ZO-Z l 7.5 7.0-1 1 210-5 7.0-8 Z0-8 Z0-3 (L5 8.l 20-5 ZO-l 20-3 0 (l 0 ().l 8.6 Tr 0 0 l) ()il 2 7.0- 7.0-7 7.0-! Product of Ex. 4 PVA 2 8.2 None None None 7.0-l7 7.0- ZO-l l ZO-Zll 7.0-) 7.0-]

l 8.0 ZO-l l 7.0-9 7.0-10 7.0-1 l 7.0-4 'l'r 0.5 7.7 70-10 -6 20-9 ZO-S 'lr l) 0.] 7.6 20-5 7.0-3 ZO-Z Tr t) 0 Acrylic 2 24.3 20-15 7.0-8 20- I 0 20- l 4 20-6 ZO-Z l 8.4 20-6 7.0-: 7.0-2 0 0 o 0.5 8.6 7.()-l 0 o (l o (1 Oil 2 7.0-4 ZO-X 7.0-7 Product of Ex. 5 PVA 2 8.4 Slight None None ZO-ltl 20-9 Z0-ltl ZO-l5 Z0-l5 20-5 Acrylic 2 x5 20- l 3 20-) 20- l 0 Z0 1 (1 20-1 1 ZO-S Oil 2 None ZO-lU ZO-H) 7.03 Product of Ex. 6 PVA 2 8.? None None None 2046 7.0-9 Z0-l2 ZO-l7 ZO-lS 7.0-7 Acrylic 2 .l Z0-l5 ZO-9 ZO-IZ Z0-l7 ZO-l4 ZO-5 Oil 2 ZO-X 7.0-8 7.0-4 Comparative Examples S-Hydroxymethyl-l-aza- PVA 2 7.5 None None None 7.0-3 7.0-4 7.0-1 ZO-4 20-2 3,7-dioxahicyclo Acrylic 2 8.4 20-] l 7.0-3 7.0-4 7.0-6 t) (3 3,l))octune (51.27: Oil 2 O 'lr 0 aqueous solution) 5-1 3 (Dow PVA 2 7.5 None None None Z0-l3 O 0 20-14 20-19 20-11 Chemical Co.) Acrylic 2 0.1 ZO-l3 0 7.0-20 20-1 1 ZO-5 Oil 2 20-20 20-10 20-6 Bis(phcnylmercuric)- PVA 2 7.0 None None None ZO-l9 ZO-l l 7.0-) 20-13 20-10 20-15 dodecenyl succinatc Acrylic Z 9.!) ZO-l7 7.0-13 7.0-8 ZO-lt) ZO-3 ZO-IO (Super Ad-it) Oil 2 Z0- 1 7 Z0-6 ZO- l4 (Tenneco Chemicals.

Inc. None PVA 75 None None None (l U 0 t) t) 0 Acrylic 9.3 O 0 (J (l (l 0 Oil U (l 0 The superiority as biocides for surface-coating com- (i compounds h vin he structural formula positions of the polyoxymethyleneoxazolidmes of this i..,\ ulu invention over a closely-related substituted oxazolldlne 4O 4 is apparent from a comparison of the blocidal data for Z the products of Examples l3 with those for 5- I hydroxymethyl-1-aZa-3,7-d1oxab1cyclo( 3 ,3 ,0 )octane. u o The products of Examples 1 and 2, which are mixtures of substituted oxazolidines that contain the comparator S-hydroxymethyl-l-aza-3,7-dioxabicyclo(3,3,0)octane gt 1-;

as well as the 5hydroxymethylpolyoxymethylene-laza-3,7-dioxabicyclo(3,3,0)octanes of this invention, were substantially more effective against bacteria and fungi than the comparator. Similarly, it is shown in the table that the product of Example 3 is more active at the 0.5% level in the PVA paint and at the 1% level in the acrylic paint than the comparator at the 2% level.

Each of the other polyoxymethyleneoxazolidines disclosed herein can be used in a similar way to protect surface-coating compositions from attack by bacteria wherein each R represents hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, halophenyl or (C- H O),,,CH OH; m represents a number in the range of O to 2; and n represents a number in the range of 1 to 4;

ii. compounds having the structural formula What is claimed is: l. A surface-coating composition having improved Cil resistance to attack by bacteria and fungi that comi prises (a) a water-insoluble, film-forming, resinous R binder selected from the group consisting of synthetic wherein each R represents alkyl of l to 6 ca b linear addition polymers prepared by the emulsion poatoms or -CH OH and R and n have the aforelymerization of ethylenically-unsaturatcd monomers, 6g mentioned significance; and oleoresinous binders, and mixtures thereof and (b) 0.1 iii mixtums th f percent to 3 percent, ase on he weight of the com- 2. A surface-coating composition as defined in claim position of a biOCidal mp n pr ing il p lyox- 1 that comprises an aqueous composition that contains ymethyleneoxazolidine selected from the group con- 10 percent to 60 percent by weight ofa synthetic linea sisting of addition polymer.

3. A surface-coating composition as defined in claim 2 wherein the synthetic linear addition polymer is polyvinylacetate.

4. A surface-coating composition as defined in claim 2 wherein the synthetic linear addition polymer is an acrylate polymer.

5. An aqueous surface-coating composition as defined in claim 2 wherein the polyoxymethyleneoxazolidine has a total of not more than six oxymcthylene (CH O) units in its ring substituents.

6. A surface-coating composition as defined in claim 1 wherein the biocidal component comprises a polyoxymethyleneoxazolidine having the structural formula wherein n represents a number in the range of l to 4.

7. A surface-coating composition as defined in claim 6 wherein the biocidal component comprises 3- hydroxymethyloxymethylene-4,4-dimethyloxazolidine.

8. A surface-coating composition as defined in claim 6 wherein the biocidal component comprises 3hydroxymethyldi(oxymethylene)]-4,4-dimethyloxazolidine.

9. A surface-coating composition as defined in claim 6 wherein the biocidal component comprises 3- [hydroxymethyltri(oxymethylene)]-4,4- dimethyloxazolidine.

10. A surface-coating composition having improved resistance to attack by bacteria and fungi that comprises (a) a water-insoluble, film-forming, resinous binder selected from the group consisting of synthetic linear addition polymers prepared by the emulsion polymerization of ethylenically-unsaturated monomers, oleoresinous binders, and mixtures thereof and (b) 0.1 percent to 3 percent, based on the weight of the composition, of a biocidal component comprising a polyoxymethyleneoxazolidine having the structural formula t'n ou'n oi cn on l t. -("ll l l R R wherein n represents a number in the range of l to 4.

12. A surface-coating composition as defined in claim 11 wherein the biocidal component comprises 5-[hydroxymethyl'di(oxymethylene)l-1-aza-3,7-dioxabicyelo(3,3,0)octane.

13. A surface-coating composition as defined in claim 11 wherein the biocidal component comprises 5-[ hydroxymethyl-tri(oxymethylene)1- l -aza-3,7-dioxabicyclo(3,3,())ctane.

14. A surface-coating composition as defined in claim 11 wherein the biocidal component comprises -[hydroxymethyltetra(oxymethylene)]-l-aza-3,7- dioxabicyclo(3,3,0)octane.

15. The method of controlling the growth of bacteria and fungi in a surface-coating composition that comprises a water-insoluble, film-forming, resinous binder selected from the group consisting of synthetic linear addition polymers prepared by the emulsion polymerization of ethylenieally-unsaturated monomers, oleoresinous binders, and mixtures thereof that comprises incorporating in said composition 0.1 percent to 3 percent, based on the weight of said composition, of a biocidal component that comprises a polyoxymethyleneoxazolidine selected from the group consisting of a. compounds having the structural formula i R R wherein each R represents hydrogenfalkyl of l to 6 carbon atoms, phenyl, halophenyl, or (C- H O),,,CH OH; m represents a number in the range of 0 to 2; and n represents a number in the range of l to 4;

b. compounds having the structural formula 1lOCil (OCil N\ 6 on it wherein each R represents alkyl of l to 6 carbon atoms or CH OH and R and n have the aforementioned significance; and

0. mixtures thereof.

16. The method of claim 15 wherein the surfacecoating composition comprises an aqueous composition that contains 10 to 60 percent by weight of a synthetic linear addition polymer.

component is an aqueous solution that contains 40 to 60 percent by weight of said polyoxymethyleneoxazolidine. 

1. A SURFACE-COATING COMPOSITION HAVING IMPROVED RESISTANCE TO ATTACK BY BACTERIA AND FUNGI THAT COMPRISES (1) A WATER-INSOLUBLE, FILM-FORMING, RESINOUS BINDER SELECTED FROM THE GROUP CONSISTING OF SYNTHETIC LINEAR ADDITION POLYMERS PREPARED BY THE EMULSION POLYMERIZATION OF ETHYLENICALLY: UNSATURATE MONOMERS, OLEORESINOUS BINDERS, AND MIXTURES THEREOF AND (B) 0.1 PERCENT TO 3 PERCENT, BASED ON THE WEIGHT OF THE COMPOSITION OF A BIOCIDAL COMPONENT COMPRISING A POLYOXYMETHYLENEOXAZOLIDINE SELECTED FROM THE GROUP CONSISTING OF (I) COMPOUNDS HAVING THE STRUCTURAL FORMULA
 2. A surface-coating composition as defined in claim 1 that comprises an aqueous composition that contains 10 percent to 60 percent by weight of a synthetic linear addition polymer.
 3. A surface-coating composition as defined in claim 2 wherein the synthetic linear addition polymer is polyvinylacetate.
 4. A surface-coating composition as defined in claim 2 wherein the synthetic linear addition polymer is an acrylate polymer.
 5. An aqueous surface-coating composition as defined in claim 2 wherein the polyoxymethyleneoxazolidine has a total of not more than six oxymethylene (-CH2O-) units in its Ring substituents.
 6. A surface-coating composition as defined in claim 1 wherein the biocidal component comprises a polyoxymethyleneoxazolidine having the structural formula
 7. A surface-coating composition as defined in claim 6 wherein the biocidal component comprises 3-hydroxymethyloxymethylene-4,4-dimethyloxazolidine.
 8. A surface-coating composition as defined in claim 6 wherein the biocidal component comprises 3hydroxymethyldi(oxymethylene))-4,4-dimethyloxazolidine.
 9. A surface-coating composition as defined in claim 6 wherein the biocidal component comprises 3-(hydroxymethyltri(oxymethylene))-4,4-dimethyloxazolidine.
 10. A surface-coating composition having improved resistance to attack by bacteria and fungi that comprises (a) a water-insoluble, film-forming, resinous binder selected from the group consisting of synthetic linear addition polymers prepared by the emulsion polymerization of ethylenically-unsaturated monomers, oleoresinous binders, and mixtures thereof and (b) 0.1 percent to 3 percent, based on the weight of the composition, of a biocidal component comprising a polyoxymethyleneoxazolidine having the structural formula
 11. A surface-coating composition as defined in claim 10 wherein the biocidal component comprises a polyoxymethyleneoxazolidine having the structural formula
 12. A surface-coating composition as defined in claim 11 wherein the biocidal component comprises 5-(hydroxymethyl-di(oxymethylene))-1-aza-3,7-dioxabicyclo(3,3,0)octane.
 13. A surface-coating composition as defined in claim 11 wherein the biocidal component comprises 5-(hydroxymethyl-tri(oxymethylene))-1-aza-3,7-dioxabicyclo(3,3,0)octane.
 14. A surface-coating composition as defined in claim 11 wherein the biocidal component comprises 5-(hydroxymethyltetra(oxymethylene))-1-aza-3,7-dioxabicyclo(3,3, 0)octane.
 15. The method of controlling the growth of bacteria and fungi in a surface-coating composition that comprises a water-insoluble, film-forming, resinous binder selected from the group consisting of synthetic linear addition polymers prepared by the emulsion polymerization of ethylenically-unsaturated monomers, oleoresinous binders, and mixtures thereof that comprises incorporating in said composition 0.1 percent to 3 percent, based on the weight of said composition, of a biocidal component that comprises a polyoxymethyleneoxazolidine selected from the group consisting of a. compounds having the structural formula
 16. The method of claim 15 wherein the surface-coating composition comprises an aqueous composition that contains 10 to 60 percent by weight of a synthetic linear addition polymer.
 17. The method of claim 16 wherein the biocidal component is an aqueous solution that contains 20 to 80 percent by weight of said polyoxymethyleneoxazolidine.
 18. ThE method of claim 16 wherein the biocidal component is an aqueous solution that contains 40 to 60 percent by weight of said polyoxymethyleneoxazolidine. 